Treatment of textile material



Patented May 10, 1949' r TREATMENT OF TEXTILE MATERIAL Donald H. Powers,Winchester, and Elmer H. Rossin, Melrose, Mass., assignors to MonsantoChemical Company, St. Louis, Mo., a corporation of Delaware No Drawing.Application December 1, 1945, Serial No. 632,285

12 Claims.

- This invention relates to improved textile finishing materials, andmethods of treating yarns and fabrics therewith.

It is common practice to treat yarns and fabrics with starch solutionsin order to impart a relatively stiffened finish thereto. Starchedfabrics however lose their stiffened character and appearance after asingle washing, and also tend to dust out. In the case of yarns thestarch is applied primarily as a size for assisting in the weavingoperation, but here also the effect of the starch is markedly diminishedby the unstable character of the coating.

It is a primary object of the present invention to provide asubstantially permanent stiffened finish on fabrics which cannot beappreciably removed by ordinary washing operations and is substantiallyfree of dusting. A further object of the invention is to provide amethod of finishing fabrics which involves applying the finishing agentto the warp yarns prior to weaving, whereby the weaving operation isfacilitated and a suitably finished fabric is obtained without furthertreatment.

In accomplishing the above objects the yarn or fabric is treated with anaqueous solution or dispersion of an ammonium or amine salt ofcopolymerized styrene, maleic anhydride and a Water-soluble orwater-dispersible thermosetting resin of the aldehyde condensation type,after which the yarn or fabric is heated. This causes the styrene maleicanhydride copolymer to react with the thermosetting resin, therebyinsolubilizing the copolymer so that most of it remains on the fabricafter washing and provides a substantially permanent finish. Thethermosetting resins which may be used for the purposes of thisinvention include the aldehyde condensation prodnets of urea, thiourea,melamine and dicyandiamide, the alkyl ether derivatives of thesecondensation products, such as the methyl, ethyl and butyl ethers, andthe aldehyde condensation products of phenols, such as phenol, cresoland resorcinol, and the like. Of the above materials, the phenolaldehyde condensation products are somewhat less desirable because ofthe discolorizing effect they produce on the yarn or fabric. However,they may be used satisfactorily on heavy industrial fabrics, such asharvester ducks, tenting material, awning material and the like. Thethermosetting resins used should be in the form of a water-soluble orwater-dispersible monomer or low polymer, i. e. they should besubstantially unpolymerized. Suitable ammonium or amine salts of thecopolymer include the salts of ammonia, guanidine, alkylamines, such asmethyl, butyl and amyl amine, and quaternary ammonium hydroxides, suchas phenyl trimethyl ammonium hydroxide.

In treating the fabric in the manner described above, it is preferableto keep the solution or bath below 180 F. to avoid appreciable reactiontaking place during the impregnation of the fabric. However, the bathmay be kept at somewhat higher temperatures for short periods withoutharmful effect. Upon removal from the bath. the fabric is heated at anelevated temperature until it is dry. Preferably, the fabric is heatedat 250 to 300 F'., but satisfactory results may be obtained attemperatures as low as 200 F. The concentration of the styrene maleicsalt in the bath and the pick-up should be adjusted to deposit on thefabric from 2 to 15% by weight of the styrene maleic salt, butpreferably between about 4 and 7%. The thermosetting resin is ordinarilyadded in amounts varying between 2 and 20% on the weight of the styrenemaleic salt.

Instead of using solutions containing both the anhydride salt and thethermosetting resin, separate solutions of the two ingredients may beprepared, after which the yarn or fabric may be treated in any order orsimultaneously therewith. It is desirable to have the bath or solutionat slightly elevated temperatures to insure uniform penetration, butgood results may also be obtained with the bath at room temperatures.

The copolymer of styrene and maleic anhydride used in accordance withthis invention is a wellestablished product which may be prepared inseveral ways. One of the well-known methods is mass polymerization,which involves heating styrene and maleic anhydride at temperaturesbetween about and 300 F. for several hours or more. Preferably, thematerials are heated cautiously, as in a water bath. Another methodwhich may be used is known as the solvent process which involvesreacting the styrene and maleic anhydride at slightly elevatedtemperatures in the presence of a solvent which is capable of dissolvingboth the starting materials and the finished polymer, such as acetone.If desired, the copolymerization may be carried out in the presence of acatalyst, such as benzoyl peroxide.

The copolymer of styrene and maleic anhydride produced by either of theabove or by any other well-known method of manufacture is soluble inacetone, but insoluble in alcohol or benzene, and forms water-solublesalts of ammonia or alkali metals. Instead of styrene, substitutedstyrenes, such as methyl or butyl styrene.

vinyl methyl ketone, acrylic esters and the like.

A further understanding of the invention will be obtained from thefollowing examples, the parts being given by weight:

Example I A solution of an ammonium salt of styrene maleic anhydrideresin was prepared by mixing together 600 parts of styrene maleicanhydride, prepared by copolymerizing equimolecular quantities ofstyrene and maleic anhydride at about 200 F. in a water bath, 400 partsof 26% NH4OH and 9000 parts of water. The resulting mixture was thenheated to 200 to 212 F. with stirring, and maintained at thistemperature until a uniform, somewhat viscous transparent solutionresulted. This required about one hour. After cooling the solution toabout 120 F., the methyl ether of tetramethylol melamine was added tothe extent of about 6% on the weight of the styrene maleic anhydrideused.

Heavy cotton sheeting was dipped in the bath prepared as describedabove, after which it was passed through a padder adjusted for 100%pickup. The bath was maintained at about 120 F. during the treatment ofthe fabric to insure uniform penetration. The treated sheeting was thenheated for about two and a half minutes on a tenter frame using hot airat 300 F., at which time it was substantially dry. The dry sheeting waswashed for one hour at the boil in a running suds, and was found toretain 90% of the deposited resin.

Example II A solution of an ammonium salt of styrene maleic anhydrideresin, containing 6% by weight of the butyl ether of tetramethylolmelamine was prepared as described in Example I. The resulting solutionwas then poured into the size box of a slasher, after which a warp of18/single cotton yarn was passed through the solution and dried on drycans in the usual manner, using 12 pounds of steam. The treated yarn wasthen rolled up on a beam and woven. Excellent Weaving was obtained andthe resulting fabric possessed a desirably stiffened finish whichretained its stiffened character even after washing. Moreover. thefabric had an unusually smooth feel and did not dust out.

Example III A solution of an ammonium salt of styrene maleic anhydrideresin was prepared by mixing together 500 grams of copolymerized styrenemaleic anhydride, 500 grams of 26% NH4OH and 9000 cubic centimeters ofwater. The resulting mixture was then heated to 200 to 212 F. withstirring. and maintained at this temperature until a uniform, somewhatviscous transparent solution resulted. which required about one hour.After cooling the solution to about 100 F.. trimethylol melamine wasadded to the extent of about on the weight of the styrene maleicanhydride used.

water.

Heavy cotton sheeting was dipped in the bath prepared as describedabove, after which itwas passed through a padder adjusted for pickup.The bath was maintained at about 100 F. during the treatment of thefabric to insure uniform penetration. The treated sheeting was thenheated for about two and a half minutes on a tenter frame using hot airat 300 F., at the end of which time it was substantially dry. The drysheeting was washed for one hour at the boil in a running suds, and wasfound to retain 92% of the deposited resin.

Example IV A solution of an ammonium salt of styrene maleic anhydrideresin was prepared as described in Example I, and diluted with an equalamount of To this was then added mono methylol urea in an amountsufficient to provide about 8% on the weight of the styrene maleicanhydride used. Spun viscose rayon was dipped in the resulting bath.after which it was passed through a padder adjusted for 100% pick-up.The bath was maintained at about 100 F. during the treatment of thefabric to insure uniform penetration.

The treated rayon was then heated for about two and a half minutes ondry cans maintained at about 240 F., at the end of which time it wassubstantially dry. The resulting fabric was smooth and full and somewhatstiffened, and retained these characteristics after several washings,

Example V Samples of acetate rayon, nylon and glass yarns were treatedin the same manner as the cotton yarn in Example II. In each case auniformly sized warp was obtained which was readily woven. The resultingfabrics were smooth, full and somewhat stiffened and retained thesecharacteristics after washing.

Although the examples refer to the treatment of cotton, viscose rayon,acetate rayon, nylon and glass, equally good results can be obtainedwith linen, flax, hemp, jute, ramie, wool, silk, cuprammonium rayon,various other synthetic textile materials, such as Vinyon and Aralac,and mixtures or blends of any of the above materials.

By treating fabrics with the finishing agents described herein, asubstantially permanent, stiffened finish is obtained, due to the factthat only relatively small amounts of the dried and reacted resin arelost on washing, i. e, of the order of 5 to 12%. The finished fabric isalso smooth and substantially free of dusting in contrast to thewell-known starch treated fabrics. When the resin is applied to the warpyarn and insolubilized thereon, there is the further advantage that theweaving operation is improved owing to the higher tensile strength ofthe yarn, its increased resistance to abrasion, and its generallystiffened character. The fabric from treated yarn may have the desiredfinish characteristics without further treatment, but if desired it maybe subjected to additional finishing operations.

It is customary to apply the sizing or finishing materials describedherein to yarns or fabrics. However, it is possible to obtain similarresults by treating fibers, either initially or at any stage of theirprocessing prior to spinning, after which the fibers may be spun andwoven to obtain fabrics of the desired finish characteristics. preparedfrom such treated fibers may also be readily woven. It is also possibleto treat in accordance with this invention fibers which are to Yarns beused as such, as for example in cotton batting, or in the preparation ofnon-woven fabrics.

It is believed that the reaction between the polymerized styrene maleicanhydride salt and the thermosetting resin involves or consists of across linking between the styrene maleic anhydride polymer and thethermosetting resin. It should be understood however that the inventionis not predicated on this or any other similar theory, and regardless ofthe type of reaction which takes place the polymeric resin salt becomesinsolubilized on the yarn or fabric with the formation of a relativelypermanent'size or finish. It should also be understood that the aqueoussolutions referred to in the appended claims are intended to includeaqueous dispersions, as it is possible that the ammonium or amine saltsand in some instances the thermosetting resins in the solution areactually present in the form of a colloidal dispersion.

What we claim is:

1. The method of finishing textile fabrics which comprises treating thefabric with an aqueous solution of an ammonium salt of copolymerizedstyrene-maleic anhydride and a water-soluble alkyl ether of methylolmelamine, said salt being deposited on the fabric in amounts varyingfrom 2 to 15% by weight. said ether being added in amounts varyingbetween 2 and 20% on the weight of said salt, and then drying thefabric, whereby said treating agents react to form an insoluble resinthereon.

2. The method of finishing textile fabrics which comprises treating thefabric with an aqueous solution of an ammonium salt of copolymerizedstyrene-maleic anhydride and a water-soluble methylol melamine, saidsalt being deposited on the fabric in amounts varying from 2 to 5% byweight, said methylol melamine being added in amounts varying between 2and 20% on the weight of said salt, and then drying the fabric, wherebysaid treating agents react to form an insoluble resin thereon.

3. The method of finishing textile fabrics which comprises treating thefabric with an aqueous solution of an ammonium salt of copolymerizedstyrene-maleic anhydride and a water-soluble condensation product ofdicyandiamide and formaldehyde, said salt bung deposited on the fabricin amounts varying from 2 to by weight, said condensation product beingadded in amounts varying between 2 and on the weight of said salt, andthen drying the fabric, whereby said treating agents react to form aninsoluble resin thereon.

4. The method of finishing textile fabrics which comprises treating thefabric with an aqueous solution of an ammonium salt of copolymerizedstyrene-maleic anhydride and a material from the group consisting ofwater-soluble thermosetting condensation products of an aliphaticaldehyde and a compound of the group consisting of urea, thiourea,melamine and dicyandiamide, the alkyl ethers of said condensationproducts, and water-soluble thermosetting condensation products of analiphatic aldehyde and a phenol, said salt being deposited on the fabricin amounts varying from 2 to 15% by weight, said condensation productbeing added in amounts varying between 2 and 20% on the weight of saidsalt, and then drying the fabric, whereby said treating agents react toform an insoluble resin thereon.

5. The method substantially as described in claim 4, but furthercharacterized in that the fabric is impregnated with the solution at atemperature below F. and is dried by heating for a short period of timeat temperatures between 200 and 300 F.

6. The method of finishing textile fabrics which comprises treating thefabric with an aqueous solution of a material from the group con sistingof water-soluble thermosetting condensation products of an aliphaticaldehyde and a compound of the group consisting of urea, thiourea,melamine and dicyandiamide, the alkyl ethers of said condensationproducts, and watersoluble thermosetting condensation products of analiphatic aldehyde and a phenol, and a salt of copolymerizedstyrene-maleic anhydride selected from the group consisting of ammoniumsalts and amine salts, said salt being deposited on the fabric inamounts varying from 2 to 15% by weight, said condensation product beingadded in amounts varying between 6 and 10% on the weight of said salt,and then drying the fabric, whereby said treating agents react to forman insoluble resin on the fabric.

7. The method of preparing and finishing textile fabrics which comprisestreating warp yarn with an aqueous solution of a material from the groupconsisting of water-soluble thermosetting condensation products of analiphatic aldehyde and a compound of the group consisting of urea,thiourea, melamine and dicyandiamide, the alkyl ethers of saidcondensation products, and Watersoluble thermosetting condensationproducts of an aliphatic aldehyde and a phenol, and a salt ofcopolymerized styrene-maleic anhydride selected from the groupconsisting of ammonium salts and amine salts, said salt being depositedon the fabric in amounts varying from 2 to 15% by Weight, saidcondensation product being added in amounts varying between 2 and 20% onthe weight of said salt, then drying the yarn, whereby said treatingagents react to form an insoluble resin thereon, and weaving theresulting yarn into a fabric.

8. The method of sizing textile warp yarns, which comprises treatingsaid yarns with an aqueous solution of a material from the groupconsisting of water-soluble thermosetting condensation products of analiphatic aldehyde and a compound of the group consisting of urea,thiourea, melamine and dicyandiamide, the alkyl ethers of saidcondensation products, and watersoluble thermosetting condensationproducts of an aliphatic aldehyde and a phenol, and a salt ofcopolymerized styrene-maleic anhydride selected from the groupconsisting of ammonium salts and amine salts, said salt being depositedon the fabric in amounts varying from 2 to 15% by weight, saidcondensation product being added in amounts varying between 2 and 20% onthe weight of said salt, and then drying the yarn, whereby said treatingagents react to form an insoluble resin thereon.

9. In the manufacture of textile yarns and fabrics from fibrousmaterials, the steps of treating said fibrous materials at some stage oftheir processing prior to spinning with an aqueous solution of amaterial from the group consisting of water-soluble thermosettingcondensation products of an aliphatic aldehyde and a compound of thegroup consisting of urea, thiourea, melamine an dicyandiamide, the alkylethers of said condensation products, and water-soluble thermosettingcondensation products of an aliphatic aldehyde and a phenol, and a saltof copolymerized styrene-maleic anhydride selected from the groupconsisting of ammonium salts and amine salts, said salt being depositedon the fabric in amounts varying from 2 to 15% by weight, saidcondensation product being added in amounts varying between 2 and 20% onthe weight of said salt, and then drying the fibers thus treated,whereby said treating agents react to form an insoluble resin thereon.

10. The method of sizing or finishing textile materials, such as fibers,yarns and fabrics which comprises treating said material with an aqueoussolution of a material from the group consisting of water-solublethermosetting condensation products of an aliphatic aldehyde and acompound of the group consisting of urea, thiourea, melamine anddicyandiamide, the alkyl ethers of said condensation products, andwater-soluble thermosetting condensation products of an aliphaticaldehyde and a phenol, and a salt of a copolymer prepared bycopolymerizing a substance selected from the group consisting of styreneagents react to form an insoluble resin thereon.

11. A finishing composition for textile fibers,

yarns or fabrics which comprises an aqueous solution of a material fromthe group consisting of water-soluble thermosetting condensationproducts of an aliphatic aldehyde and a compound of the group consistingof urea, thiourca, melamine and dicyandiamide, the alkyl ethers of saidcondensation products, and water-soluble thermosetting condensationproducts of an aliphatic aldehyde and a phenol, and a salt ofcopolymerized styrene-maleic anhydride selected from the groupconsisting of ammonium salts and amine salts, said solution containingan amount of said condensation product varying from 6 to 10% of theamount of said salt.

12. A textile fabric impregnated with a salt of copolymerizedstyrene-maleic anhydride selected from the group consisting of ammoniumsalts and amine salts, which salt has been cross-linked with a materialfrom the group consisting of water-soluble thermosetting condensationproducts of an aliphatic aldehyde and a compound of the group consistingof urea, thiourea, melamine and dicyandiamide, the alkyl ethers of-saidcondensation products, and water-soluble thermosetting condensationproducts of an aliphatic aldehyde and a phenol, said salt beingdeposited on the fabric in amounts varying from 2 to 15% I by weight,said condensation product being added in amounts varying between 2 and20% on the weight of said salt.

DONALD H. POWERS. ELMER H. ROSSIN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,227,200 Roble Dec. 31, 19402,245,491 Menger et al June 10, 1941 2,299,786 Battye et a1 Oct. 27,1942 2,301,959 Lanning Nov. 17, 1942 2,374,767 Mitchell et al May 1,1945

